EP3635019B1 - Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul - Google Patents
Polypropylene mit breiter molekulargewichtsverteilung und hohen schmelzflussraten und hohem biegemodul Download PDFInfo
- Publication number
- EP3635019B1 EP3635019B1 EP18730483.7A EP18730483A EP3635019B1 EP 3635019 B1 EP3635019 B1 EP 3635019B1 EP 18730483 A EP18730483 A EP 18730483A EP 3635019 B1 EP3635019 B1 EP 3635019B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polypropylene
- reactor
- catalyst
- previous
- polypropylenes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004743 Polypropylene Substances 0.000 title claims description 129
- -1 polypropylenes Polymers 0.000 title claims description 107
- 229920001155 polypropylene Polymers 0.000 title claims description 102
- 238000009826 distribution Methods 0.000 title description 6
- 239000003054 catalyst Substances 0.000 claims description 46
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 23
- 230000007547 defect Effects 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 description 18
- 239000000306 component Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
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- 239000000523 sample Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
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- 150000002681 magnesium compounds Chemical class 0.000 description 8
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
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- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
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- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
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- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
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- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- SZIZIGBTHTUEBU-UHFFFAOYSA-N dimethoxy-bis(4-methylphenyl)silane Chemical compound C=1C=C(C)C=CC=1[Si](OC)(OC)C1=CC=C(C)C=C1 SZIZIGBTHTUEBU-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
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- 229920002521 macromolecule Polymers 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- 238000012856 packing Methods 0.000 description 2
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- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- GJJVAFUKOBZPCB-ZGRPYONQSA-N (r)-3,4-dihydro-2-methyl-2-(4,8,12-trimethyl-3,7,11-tridecatrienyl)-2h-1-benzopyran-6-ol Chemical class OC1=CC=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-ZGRPYONQSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 description 1
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- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
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- KVSQODQSFPXWBD-UHFFFAOYSA-N dibutyl(ethoxy)alumane Chemical compound CCCC[Al](OCC)CCCC KVSQODQSFPXWBD-UHFFFAOYSA-N 0.000 description 1
- CGYGEZLIGMBRKL-UHFFFAOYSA-N dicyclohexyl(diethoxy)silane Chemical compound C1CCCCC1[Si](OCC)(OCC)C1CCCCC1 CGYGEZLIGMBRKL-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- AAMBIAPMLISIDH-UHFFFAOYSA-N dimethoxy-bis(2-methylphenyl)silane Chemical compound C=1C=CC=C(C)C=1[Si](OC)(OC)C1=CC=CC=C1C AAMBIAPMLISIDH-UHFFFAOYSA-N 0.000 description 1
- IWEAAVHEPCUQHR-UHFFFAOYSA-N dimethoxy-bis(3-methylphenyl)silane Chemical compound C=1C=CC(C)=CC=1[Si](OC)(OC)C1=CC=CC(C)=C1 IWEAAVHEPCUQHR-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- DHRQKFYLKJURNK-UHFFFAOYSA-N dodecoxycarbonyloxy dodecyl carbonate Chemical compound CCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCC DHRQKFYLKJURNK-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 238000007730 finishing process Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WMZJAVHBMXPTRD-UHFFFAOYSA-N icosoxycarbonyloxy icosyl carbonate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCCCCCC WMZJAVHBMXPTRD-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- RVOYYLUVELMWJF-UHFFFAOYSA-N magnesium;hexane Chemical compound [Mg+2].CCCCC[CH2-].CCCCC[CH2-] RVOYYLUVELMWJF-UHFFFAOYSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 238000001175 rotational moulding Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 description 1
- JHVNMGWNEQGGDU-UHFFFAOYSA-N tert-butyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C(C)(C)C)OCC JHVNMGWNEQGGDU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- DBOCOZGDGUWSNE-UHFFFAOYSA-N tetracosoxycarbonyloxy tetracosyl carbonate Chemical compound C(=O)(OCCCCCCCCCCCCCCCCCCCCCCCC)OOC(=O)OCCCCCCCCCCCCCCCCCCCCCCCC DBOCOZGDGUWSNE-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229930003802 tocotrienol Natural products 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 229940068778 tocotrienols Drugs 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
Definitions
- the present invention relates to polypropylenes having a broad molecular weight distribution and high melt flow rate that maintain a high flexural modulus.
- a polypropylene comprising within a range from 0 wt% to 4 wt% ethylene and/or C4 to C12 ⁇ -olefin derived units, having a melt flow rate (MFR, 230°C/2.16kg) greater than 20 g/10 min; an Mz/Mw of 4 to 7; a Mw/Mn of 14 to 22; and a flexural modulus of at least 250 (1720 MPa), or 280 (1930 MPa), or 300 kpsi (2070 MPa) (0.5 in/min ASTM D790(A)), wherein the polypropylene is reactor grade.
- MFR melt flow rate
- 230°C/2.16kg a
- MFR melt flow rate
- reactor grade polypropylenes comprising within a range from 0 wt% to 2, or 4 wt% ethylene and/or C4 to C12 ⁇ -olefin derived units, having:
- the inventive polypropylenes can be described by any number of other features, and/or produced in a number of ways.
- the polypropylenes have a number average molecular weight (Mn) of at least 10 kg/mole, or within a range from 10 to 35 kg/mole.
- the polypropylenes have a weight average molecular weight (Mw) of at least 100 kg/mole, or within a range from 100, or 150 to 600, or 650, or 700, or 800 kg/mole.
- the polypropylenes have a z-average molecular weight of at least 900, or 1000 kg/mole, or within a range from 900, or 1000 to 2,000, or 2,200, or 2,400, or 2,600 kg/mole.
- the polypropylenes also have an Mw/Mn value within a range from 14 to 22. In any embodiment, the polypropylenes have an Mz/Mn value of greater than 4, or 10, or 20, or 50, or within a range from 4, or 10, or 20, or 50 to 110, or 120. In any embodiment, the polypropylene also has an Mz+1 value of at least 4,800, or 5,000 kg/mole, or within a range from 4,800, or 5,000 kg/mole to 6,000, or 6,500 kg/mole.
- the Mz/Mw value for the polypropylene is within a range of 4, or 4.5 to 6.5, or 7 within an MFR range from 10, or 20 g/10 min to 100 g/10 min.
- the polypropylenes may have certain desirable thermal properties as well.
- the polypropylenes have a melting point temperature (T m ) of at least 156, or 158, or 160°C, or within a range from 156, or 158, or 160°C to 168, or 170, or 174°C.
- T c crystallization temperature
- the polypropylene has a heat deflection temperature (HDT) of at least 120, or 122°C, or within a range from 120, or 122°C to 130, or 134, or 140°C. These are the values without added nucleator.
- HDT heat deflection temperature
- the polypropylenes may have certain desirable structural properties.
- the polypropylenes have an average meso run length (MRL) of 130, or 120, or 115 or less, or within a range from 85, or 90, or 95 to 115, or 120, or 130.
- MRL average meso run length
- the polypropylenes have 80, or 85, or 90 or more stereo defects per 10,000 monomers (Ds), or within a range from 80, or 85, or 90 to 115, or 120 defects/10,000 monomers.
- the polypropylenes exhibit shear thinning.
- the complex viscosity (logarithm) of the polypropylenes as a function of angular frequency applied to the melt at 190°C possess a nearly linear (negative slope) relationship, such as shown in FIG. 3 .
- the polypropylenes possess a relatively high complex viscosity at very low frequencies (e.g., 0.01 rad/sec), but very low complex viscosity at high frequencies (e.g. 100 rad/sec).
- the polypropylenes have a complex viscosity of less than 300, or 250 Pa•s, or within a range from 250 to 400, or 500 Pa•s at 100 rad/s (190°C).
- polypropylenes have a complex viscosity of at least 2000, or 2500 Pa•s, or within a range from 2500, or 3000 Pa•s to 8000, or 10,000 Pa•s at 0.01 rad/s (190°C).
- the polypropylenes can also be described by other mechanical properties.
- the polypropylenes have an Izod impact of at least 0.2, or 0.3 ft-lb/in (23°C), or within a range from 0.2, or 0.3 to 1, or 1.2, or 2, or 2.4 ft-lb/in (23°C).
- the polypropylenes may have a tensile strength at yield within a range from 34, or 36 MPa to 42, or 44, or 46, or 48 MPa.
- the polypropylenes can be produced by any means of olefin polymerization, but are preferably produced from a single catalyst and single stage polymerization process.
- single catalyst what is meant is that the olefins are contacted with a catalyst derived from the same or similar preparation, thus having the same or similar homogeneous composition such as a single Ziegler-Natta type of catalyst, metallocene catalyst, or other catalyst.
- the single catalyst is a Ziegler-Natta catalyst with one or more external electron donors in a slurry polymerization system, preferably two external donors whose overall concentration can be varied, and/or they can be varied with respect to one another.
- the single catalyst is a Ziegler-Natta catalyst that preferably includes a solid titanium catalyst component comprising titanium as well as magnesium, halogen, at least one non-aromatic "internal" electron donor, and at least one, preferably two or more "external” electron donors.
- the solid titanium catalyst component also referred to as a Ziegler-Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound, and at least the internal electron donor.
- the titanium compound used in the preparation of the solid titanium catalyst component include tetravalent titanium compounds having the formula Ti(OR n )X 4-n , wherein R is a hydrocarbyl radical, X is a halogen atom, and n is from 0 to 4.
- a hydrocarbyl radical is defined to be C 1 to C 20 radicals, or C1 to C10 radicals, or C6 to C20 radicals, or C7 to C21 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic).
- the halogen-containing titanium compound is a titanium tetrahalide, or titanium tetrachloride.
- the magnesium compound to be used in the preparation of the solid titanium catalyst component includes a magnesium compound having reducibility and/or a magnesium compound having no reducibility. Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond.
- Suitable examples of such reducible magnesium compounds include dimethyl magnesium, diethyl-magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, magnesium ethyl chloride, magnesium propyl chloride, magnesium butyl chloride, magnesium hexyl chloride, magnesium amyl chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and/or butyl magnesium halides.
- the titanium-based Ziegler-Natta catalyst is said to be supported.
- the Ziegler-Natta catalysts are used in combination with a co-catalyst, also referred to herein as a Ziegler-Natta co-catalyst.
- a co-catalyst also referred to herein as a Ziegler-Natta co-catalyst.
- Compounds containing at least one aluminum-carbon bond in the molecule may be utilized as the co-catalysts, also referred to herein as an organoaluminum co-catalyst.
- organoaluminum compounds include complex alkylated compounds of metals of Group I of the Period Table (lithium, etc.) and aluminum represented by the general formula M 1 AlR 1 4 , wherein M 1 is the Group I metal such as Li, Na, or K, and R 1 is as defined in formula (2).
- organoaluminum compounds include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl-aluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide.
- trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum
- trialkenyl aluminums such as triisoprenyl aluminum
- dialkyl aluminum alkoxides such as diethyl-aluminum ethoxide and dibutyl aluminum ethoxide
- alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide.
- Electron donors are present with the metal components described above in forming the catalyst suitable for producing the polypropylenes described herein. Both “internal” and “external” electron donors are desirable for forming the catalyst suitable for making the polypropylene described herein. More particularly, the internal electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl. Examples of suitable internal electron donors include amines, amides, ethers, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids.
- the one or more internal donors are non-aromatic.
- the non-aromatic internal electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof.
- the non-aromatic internal electron donor(s) comprises a C1 to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid.
- the external electron donors may comprise an organic silicon compound of the general formula R 1 n Si(OR 2 ) 4-n , wherein R 1 and R 2 independently represent a hydrocarbyl radical and n is 1, 2, or 3.
- suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diiso-propyldiethoxysilane, t-butylmethyl-n-diethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyl-dimethoxysilane,
- the external electron donors are selected from any one or more of methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane cyclohexyltrimethoxysilane, tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxysilane, and/or dicyclopentyldimethoxysilane.
- the production of the polypropylene preferably includes the use of two external electron donors, most preferably simultaneously. Suitable methods for using such external electron donors is disclosed in US 6,087,459 , and US 6,686,433 .
- the two external electron donors may be selected from any of the external electron donors described herein.
- the first external electron donor has the formula R 1 2 Si(OR 2 ) 2 , wherein each R 1 is independently a C1 to C10 hydrocarbyl radical in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a C1 to C10 hydrocarbyl radical; and the second external electron donor has the formula R 3 n Si(OR 4 ) 4-n , wherein each R 3 and R 4 are independently a C1 to C10 hydrocarbyl radical, and n is 1, 2, or 3; wherein the second external electron donor is different than the first external electron donor.
- the combined concentration of external electron donors can be present with the catalyst and monomer(s) in the reactor to within a range from 10, or 20 ppm to 80, or 100, or 120 ppm.
- the concentration of the catalyst system in the polymerization may be from 0.01 to 200 millimoles, or more preferably from 0.05 to 100 millimoles, calculated as a titanium atom, per liter of an inert hydrocarbon medium.
- the organoaluminum co-catalyst may be present in an amount sufficient to produce from 0.1 to 500 g, or more preferably from 0.3 to 300 g, of a polymer per gram of the titanium catalyst present, and may be present at from 0.1 to 100 moles, or more preferably from 0.5 to 50 moles, per mole of the titanium atom present in the catalyst component.
- suitable means of polymerization include contacting the catalyst and olefins in a gas phase reactor, stirred tank reactor, loop reactor, or other reactors known in the art.
- the polymerization may take place in the gas phase, as a solution, or as a slurry.
- hydrogen may be present in the reactor to modulate the molecular weight of the polypropylene being produced.
- the hydrogen if combined with the single catalyst during the polymerization, is combined at a constant level. This means that the total concentration of hydrogen in the reactor is held constant (varying by no more than 1, or 2, or 3, or 5% of its overall level) during the production of the polypropylene.
- the polymerization is most preferably a "single stage" polymerization process, meaning that the olefins and catalyst, and optional hydrogen are contacted under the same or similar conditions throughout the production of the polypropylene, such as in a single reactor, or multiple reactors in parallel or series, held at a constant level of temperature, pressure, monomer concentration, and hydrogen concentration, where no parameter changes by more than ⁇ 2%, or ⁇ 5%, or ⁇ 10% going from one reactor to another.
- a polymerization is single stage even if performed in two or more loop slurry reactors in parallel if the reactor conditions are held at a constant level.
- slurry polymerization process or “slurry polymerization reactor” refer to a process or reactor that handles polymer that is only partly dissolved or not dissolved at all in the medium, either monomer, solvent, or both, typically having at least 20 wt% polymer suspended or not dissolved.
- catalyst components, solvent, monomers and hydrogen are passed under pressure to one or more polymerization reactors.
- Catalyst components may be passed in the inventive processes to the polymerization reactor as a mixture in aliphatic hydrocarbon solvent, in oil, a mixture thereof, or as a dry powder.
- the polymerization process is carried out using propylene as the only solvent.
- the temperature of the reactor can be controlled by the rate of catalyst addition (rate of polymerization), the temperature of the solvent/monomer feed stream and/or the use of heat transfer systems.
- reactor temperatures can range from 50 to 120°C or more, while pressures are generally higher than 300 psig, or within a range from 300 psig to 1000, or 1200 psig.
- the polymerization temperature is preferably at least 50, or 60, or 70°C, or within a range from 50, or 60, or 70, or 80, or 90, or 100, or 120°C to 130, or 140, or 150, or 160, or 170°C.
- the propylene and, if present, ethylene and/or other C4 to C12 ⁇ -olefins, are dissolved/dispersed in the solvent either prior to being passed to the polymerization reactor (or for gaseous monomers, the monomer may be passed to the reactor so that it will dissolve in the reaction mixture).
- the solvent and monomers Prior to mixing, are generally purified to remove potential catalyst poisons.
- the feedstock may be heated or cooled prior to delivery to the first reactor. Additional monomers and solvent may be added to the second reactor, and it may be heated or cooled.
- the solvent is the propylene monomer itself.
- the catalysts/activators can be passed to one polymerization reactor or split between two or more reactors. In solution or slurry polymerization, polymer produced is molten and remains dissolved or partially dissolved in the solvent under reactor conditions, forming a polymer solution.
- the catalyst may be passed to the reactor in solid form or as a slurry/suspension in a solvent. Alternatively, the catalyst suspension may be premixed with the solvent in the feed stream for the polymerization reaction. Catalyst can be activated in-line, or by an activator with which it is co-supported. In some instances premixing is desirable to provide a reaction time for the catalyst components prior to entering the polymerization reactor, but this step is preferably absent.
- the catalyst activity is preferably 20,000 kg polymer per kg of catalyst or more, more preferably 50,000 kg polymer per kg of catalyst or more, even more preferably 100,000 kg polymer per kg of catalyst or more.
- the solution or slurry polymerization processes of this disclosure includes a stirred reactor system comprising one or more stirred polymerization reactors.
- the reactors should be operated under conditions to achieve a thorough mixing of the reactants.
- the reactors may operate at the same or different temperatures and fluidly connected in series, but preferably operate at the same temperature or within ⁇ 2°C of one another.
- the residence time in each reactor will depend on the design and the capacity of the reactor.
- the two or more reactors otherwise operate under the same conditions.
- the solution or slurry polymerization process is carried out in one or more loop-type of reactors, preferably two fluidly connected in series.
- reactor systems include a single reactor and multiple reactors in series or parallel configuration, such as that disclosed in US 2007/0022768 .
- the solvent/monomer, preferably simply propylene, flow in these reactors is typically maintained using pumps and/or pressure systems, and may operate continuously by having monomer and catalyst feed at one point and extracting the forming polymer from another point, preferably downstream therefrom.
- the conditions of temperature, catalyst concentration, hydrogen concentration, and monomer concentration may be the same or different in each loop reactor and may be tailored as necessary to suit the desired end product.
- the solution polymerization process of this disclosure uses heat exchanger types of reactor where polymerization reaction takes place in the heat exchanger.
- the reactors can be one or more shell and tube type of heat exchangers, or one or more spiral type of heat exchanger.
- the polypropylene solution is then discharged from the reactor as an effluent stream and the polymerization reaction is quenched, typically with coordinating polar compounds, to prevent further polymerization.
- the polymer solution On leaving the reactor system the polymer solution is passed through a heat exchanger system on route to a devolatilization system and polymer finishing process. Under certain conditions of temperature and pressure, the polymer solution can phase separate into a polymer lean phase and a polymer rich phase.
- the polypropylene can be also recovered from the effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by stripping the solvent or other media with heat or steam.
- antioxidants can be incorporated in the polymer during the finishing procedure.
- Possible antioxidants include phenyl-beta-naphthylamine; di-tert-butylhydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2'-methylene-bis(4-methyl-6-tert-butyl)phenol, and 2,2,4-trimethyl-6-phenyl-1,2-dihydroquinoline, and/or stabilizing agents such as tocopherols or lactones, or other agents as disclosed in WO 2009/007265 .
- the inventive polypropylenes are "reactor grade” meaning that the polymers have not undergone any post-reactor process to change their chemical structure (e.g., cross-linking, branching, grafting), such as by reactive extrusion, electron-beam or ultra-violet radiation treatment, or silane grafting.
- a polypropylene is "reactor grade” if for example no byproducts of peroxide reactions (visbreaking or cross-linking/long chain branch inducing) can be detected, and no grafted moieties are detected, and no long chain branching and/or cross-linked chains are detected.
- Byproducts of peroxide reactions include alcohols and ketones and can be detected by NMR.
- Long chain branching can be determined using the intrinsic viscosity (g'vis) of a polymer, which should have a value of less than 0.98, or 0.97, or 0.96 for a branched and/or cross-linked polypropylene.
- the g'vis value for a polymer can be determined using a high temperature viscometer, in conjunction with GPC methods described further herein.
- the polypropylene produced from a single catalyst and single stage polymerization process where preferably no other process has been carried out to alter the chemical structure of the polypropylene molecules.
- the polypropylenes described herein may be subject to any number of post-reactor processing, such as reactive extrusion processes described in WO 2016/126429 A1 .
- the polypropylene is combined with an organic peroxide, especially a short half-life peroxide in a melt extrusion process to produce a branched polypropylene, such polypropylenes typically having an enhanced melt strength and extensional viscosity.
- this takes place in the absence of any additional monomers or cross-linking agents such as butadiene, 1,9-decadiene, norbornenes, or other diene-type monomers known in the art.
- Useful organic peroxides include those that are short half-life peroxides such as di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dibutyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, didodecyl peroxydicarbonate, diicosyl peroxydicarbonate, and ditetracosyl peroxydicarbonate.
- the polypropylene may be treated with a long half-life peroxide such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, di-tert-butyl peroxide, and dicumyl peroxide to effect "visbreaking" of the polypropylene as is known in the art.
- a long half-life peroxide such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, di-tert-butyl peroxide, and dicumyl peroxide to effect "visbreaking" of the polypropylene as is known in the art.
- the inventive polypropylenes find use in making many thermoformed articles such as automotive components, construction components, electronic devices, medical equipment, sports equipment, food containers, appliances, and other domestic and commercial uses.
- the polypropylenes can find use thermoformed articles made from injection molding, blow molding, and rotational molding processes.
- the polypropylenes described herein are useful in injection molding to form articles.
- the injection molding process uses a ram or screw-type plunger to force molten polymer into a mold cavity; this solidifies into a shape that has conformed to the contour of the mold. It is most commonly used to process both thermoplastic and, thermosetting polymers, with the volume used of the former being considerably higher.
- the inventive polypropylenes are useful due to characteristics which make them highly suitable for injection molding, such as the ease with which they may be recycled, their versatility allowing them to be used in a wide variety of applications, and their ability to soften and flow upon heating.
- the temperature is preferably kept below the decomposition temperature of the polypropylene, preferably within a range from 140°C to 200, or 240°C.
- thermoplastics such as the polypropylenes described herein also have an element of safety over thermosets; if a thermosetting polymer is not ejected from the injection barrel in a timely manner, chemical cross-linking may occur causing the screw and check valves to seize and potentially damaging the injection molding machine.
- Injection molding consists of high pressure injection of the raw material into a mold which shapes the polymer into the desired shape. Molds can be of a single cavity or multiple cavities. In multiple cavity molds, each cavity can be identical and form the same parts or can be unique and form multiple different geometries during a single cycle.
- thermoplastics such as the polypropylenes described herein are molded, typically pelletized material, preferably compounded with desirable additives such as antioxidants and alkyl-radical scavengers, is fed through a hopper into a heated barrel with a reciprocating screw. Upon entrance to the barrel the temperature increases and the molecular forces that resist relative flow of individual chains are weakened. This process reduces its viscosity, which enables the polymer to flow with the driving force of the injection unit.
- the screw delivers the raw material forward, mixes and homogenizes the thermal and viscous distributions of the polymer, and reduces the required heating time by mechanically shearing the material and adding a significant amount of frictional heating to the polymer.
- a “shot” is the volume of material that is used to fill the mold cavity, compensate for shrinkage, and provide a cushion (approximately 10% of the total shot volume, which remains in the barrel and prevents the screw from bottoming out) to transfer pressure from the screw to the mold cavity.
- the process normally uses a transfer position corresponding to a 95 to 98% full cavity where the screw shifts from a constant velocity to a constant pressure control. Often injection times are well under 1 second.
- the packing pressure is applied, which completes mold filling and compensates for thermal shrinkage, which is quite high for thermoplastics relative to many other materials.
- the packing pressure is applied until the gate (cavity entrance) solidifies. Due to its small size, the gate is normally the first place to solidify through its entire thickness. Once the gate solidifies, no more material can enter the cavity.
- the screw reciprocates and acquires material for the next cycle while the material within the mold cools so that it can be ejected and be dimensionally stable. This cooling duration can be reduced by the use of cooling lines circulating water or oil from an external temperature controller. Once the required temperature has been achieved, the mold opens and an array of pins, sleeves, strippers, etc. are driven forward to demold the article. Then, the mold closes and the process is repeated.
- Injection molding is used to create many articles such as packaging, food containers, bottle caps, automotive parts and components, electronics casings, beauty care products, some musical instruments (and parts of them), one-piece chairs and small tables, storage containers, consumer goods containers for such items as moist wipes and food items, mechanical parts, and most other plastic articles available. Injection molding is ideal for producing high volumes of the same article.
- Polypropylenes (hPP) having an Mz/Mw of at least 4 and an Mw/Mn of at least 10 (“BMW PP”) in a range of melt flow rates were produced in a stirred tank slurry polymerization reactor by contacting propylene, and optionally ethylene as stated in the final weight percentages in the tables below, with a Ziegler-Natta catalyst solid as described herein, triethylaluminum (TEAL), and propyltriethoxysilane and dicyclopentyldimethoxysilane as external donors, and hydrogen to a final MFR as stated in the tables.
- the reactor was operated as a single stage in that the conditions of hydrogen, temperature, external electron donor, and pressure were constant.
- Exemplary reactor conditions are as shown in Table 1.
- Table 1. Suitable Loop-Slurry Polymerization Reactor Conditions 2 MFR hPP 25 MFR hPP 35 MFR hPP Donors (wppm in propylene) 30 30 30 TEAL (wppm in propylene) 50 50 50 50 H 2 concentration (mppm) 8,000 31,000 37,000 Reaction level (inches H 2 O) 16 16 16 Reaction residence time (hours, calculated) 1.7 1.7 1.7 reaction temperature (°C) 70 70 70 70 70 70 70 70
- Reported and claimed values for Mn are ⁇ 2 kg/mole, for Mw are ⁇ 50 kg/mole, and for Mz are ⁇ 100 kg/mole.
- Mw/Mn is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), while the “Mz/Mw” is the ratio of the Mw to the Mz, an indication of the amount of high molecular weight component to the polypropylene.
- the Mw, Mn, and Mz values for the polypropylenes were determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10 ⁇ m Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 ⁇ m Teflon filter and degassed with an online degasser before entering the GPC instrument.
- TCB 1,2,4-trichlorobenzene
- BHT butylated hydroxytoluene
- the nominal flow rate is 1.0 mL/min and the nominal injection volume is 200 ⁇ L.
- the whole system including transfer lines, columns, detectors are contained in an oven maintained at 145°C.
- Given amount of polymer sample is weighed and sealed in a standard vial with 80 ⁇ L flow marker (heptane) added to it.
- polymer is automatically dissolved in the instrument with 8 mL added TCB solvent.
- the polymer is dissolved at 160°C with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples.
- the TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145°C.
- the sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
- the mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
- the conventional molecular weight (by infra-red detection) was determined by combining universal calibration relationship with the column calibration which was performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M g/mole.
- the LS detector was a Wyatt Technology High Temperature Dawn Heleos.
- ⁇ R( ⁇ ) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
- "c” is the polymer concentration determined from the DRI analysis
- a 2 is the second virial coefficient
- P( ⁇ ) is the form factor for a mono-disperse random coil
- Branching of a polypropylene is determined as follows.
- a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, was used to determine specific viscosity.
- One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
- the specific viscosity ( ⁇ s ) for the solution flowing through the viscometer was calculated from their outputs.
- the polypropylenes were characterized using GPC, the results for which are summarized in Table 2. These are from a first set of experiments. Table 2. GPC Characteristics of the polypropylenes, non-nucleated Parameter 1 MFR BMW PP 2 MFR BMW PP 25 MFR BMW PP 43 MFR BMW PP 90 MFR BMW PP Mn (kg/mole) 26.6 26.0 16.8 13.8 11.3 Mw (kg/mole 536 491 259 219 181 Mz (kg/mole) 1,912 1,770 1,399 1,308 1,019 Mw/Mn 20.1 18.9 15.4 15.8 16 Mz/Mw 3.6 3.6 5.4 6.0 5.6
- inventive polypropylenes were further characterized by other test methods. Some were nucleated with 1000 ppm sodium benzoate as indicated, otherwise were not. Two sets of experiments were performed, the first set in which the results are set forth in Table 3 (and Table 2), and the second set in which the results are set forth in Tables 4A to 4C. The "standard" commercial polypropylenes are plotted along with inventive polypropylenes from Table 3 in FIG. 1 . Blending studies with nucleators were carried out using a 57 mm extruder in the first set of experiments, and a 30 mm extruder in the second set.
- the grades of polypropylene listed as "PP####" are all from ExxonMobil Chemical Company (Houston, Texas).
- the “competitive HCPP1” is a commercial high crystallinity polypropylene homopolymer.
- standard PP refers to a polypropylene homopolymer having a Mw/Mn value of less than 5, such as between 2.5 to 3.5.
- DSC Differential Scanning Calorimetry
- Sample sizes were from 3.5 mg to 5 mg and were heated at rate of 10°C/min from -20°C to 220°C in nitrogen gas flowing at a rate of 50 ml/min.
- the samples were first cooled from 20°C to -20°C, then heated to 220°C to remove any thermal history. Then the samples were cooled from 220°C to -20°C, then heating back up from -20°C to 220°C in the second heating processes. All the DSC plots on first cooling and second heating were recorded.
- the melting point temperature, T m was recorded during the second heating and is the peak heat flow (zero inflection), and the crystallization temperature, T c , was recorded during the first cooling at the peak minimum (zero inflection).
- the Small Angle Oscillatory Spectroscopy was used to determine viscosity at low shear rates. Polymer samples were prepared using hot press (either a Carver Press or Wabash Press) to make disks of 25 mm in diameter and 2.5 mm in thickness. In order to characterize the shear thinning behavior, a rheometer ARES-G2 (TA Instruments) was used to conduct small angle oscillatory shear measurements at angular frequency ranging from 0.01 to 500 rad/s at temperature 190°C and at a fixed strain of 10%. The data was then converted into viscosity as a function of shear rate. To ensure that selected strain provides measurements within linear deformation range, the strain sweep measurements have been conducted (at angular frequency of 100 Hz). Data was processed using Trios software.
- SAOS Small Angle Oscillatory Spectroscopy
- stereo pentads Chemical shift assignments for the stereo defects (given as stereo pentads) can be found in the literature ( L. Resconi et al. in 100 CHEM. REv. 1253-1345 (2000 )).
- the stereo pentads e.g., mmmm, mmmr, mrm, etc.
- mm, mmmr and rr stereo triad distribution
- m and r mole percentage diads
- Three types of regio defects were quantified: 2,1-erythro, 2,1-threo and 3,1-insertion. The structures and peak assignments for these are also given in the reference by Resconi et al.
- MRL 10,000/D total .
- This definition of MRL is based upon the number of structural chain punctuations or defects that result from propylene insertions that have occurred in a non-regular fashion (stereo and regio defects). It does not include the punctuations due to the presence of comonomer (e.g., ethylene in a polypropylene random copolymer).
- the regio defects each give rise to multiple peaks in the carbon NMR spectrum, and these are all integrated and averaged (to the extent that they are resolved from the other peaks in the spectrum), to improve the measurement accuracy.
- the chemical shift offsets of the resolvable resonances used in the analysis are tabulated in US 7,807,769 .
- HDT Heat deflection (distortion) temperature.
- HDT was measured according to ASTM D648 using a load of 0.45 MPa (66 psi) or 1.8 MPa (264 psi) as designated.
- Tensile Strength The tensile properties such as tensile strength at yield (also referred to here as yield stress) and elongation at yield (also referred to here as yield strain) were measured as per ASTM D638, with a crosshead speed of 50.8 mm/min (2.0 in/min) and a gauge length of 50.8 mm (2.0 in), using an Instron machine.
- Izod Impact Strength The Izod impact of the polypropylenes and commercial examples was tested per ASTM D256.
- Second set of inventive and commercial polypropylene Flexural Modulus measurements Sample Description 1% Sec Mod @ 0.05 in/min (kpsi) 1% Sec Mod @ 0.05 in/min (MPa) 1% Sec Mod @ 0.5 in/min (kpsi) 1% Sec Mod @ 0.5 in/min (MPa) BMW PP (20 MFR) 337 2320 376 2590 BMW PP (20 MFR) w/ NaBz 362 2500 399 2750 BMW PP (35 MFR) 323 2230 359 2480 BMW PP (35 MFR) w/ NaBz 357 2460 396 2730 Competitive HCPP1 333 2300 368 2540 ExxonMobil TM PP3155 205 1414 - - Table 4C.
- Such additional additives can include, for example, fillers, nucleators or clarifiers, colorants, antioxidants, alkyl-radical scavengers (preferably vitamin E, or other tocopherols and/or tocotrienols), anti-UV agents, acid scavengers, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers (often referred to as hydrocarbon resins), and other additives well known in the art.
- the phrase "consisting essentially of” means that there are no other process features that will alter the claimed properties of the polymer, polymer blend or article produced therefrom by any more than 10, 15 or 20%, but there may otherwise be minor process features not named.
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Claims (11)
- Polypropylen von Reaktorqualität, das innerhalb eines Bereichs von 0 Gew.-% bis 4 Gew.-% von Ethylen und/oder C4- bis C12-α-Olefin abgeleitete Einheiten umfasst, mita) einer Schmelzflussrate (MFR, 230°C/2,16 kh) innerhalb eines Bereichs von 20 bis 500 g/10 min,b) einem Mz/Mw von 4 bis 7,c) einem Biegemodul von mindestens 250 kpi (1720 MPa) (0,5 in/min ASTM D790(A)),d) einem Mw/Mn-Wert von 14 bis 22.
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einem Mz+1-Wert von mindestens 4800 kg/Mol.
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer Schmelzpunkttemperatur (Tm) von mindestens 156°C.
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer Kristallisationstemperatur (Tc) von mindestens 116°C.
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer Wärmeformänderungstemperatur (HDT) von mindestens 120°C.
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer durchschnittlichen meso-Lauflänge (MRL) von 130 oder weniger.
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit 80 oder mehr Stereodefekten auf 10 000 Monomere (Ds) .
- Polypropylen von Reaktorqualität nach einem der vorhergehenden Ansprüche mit einer komplexen Viskosität von weniger als 300 Pa-s bei 100 rad/s (190°C) und/oder einer komplexen Viskosität von mindestens 2000 bei 0,01 rad/s Pa·s (190°C) und/oder einer Izod-Schlagfestigkeit von mindestens 0,2 ft·lb/in (23°C).
- Spritzgussartikel, der das Polypropylen von Reaktorqualität gemäß einem der vorhergehenden Ansprüche umfasst.
- Verfahren zur Herstellung von Polypropylen, das innerhalb eines Bereichs von 0 Gew.-% bis 4 Gew.-% von Ethylen und/oder C4- bis C12-alpha-Olefin abgeleitete Einheiten umfasst, bei dem Propylen und gegebenenfalls Ethylen und/oder C4- bis C12-al-pha-Olefine mit Einzelkatalysator, wobei der Einzelkatalysator ein Ziegler-Natta-Katalysator mit mindestens einem nicht-aromatischen internen Elektronendonor und einem oder mehreren externen Elektronendonoren ist, in einem einstufigen Polymerisationsverfahren in einem Aufschlämmungspolymerisationssystem kombiniert werden, und wobei Wasserstoff während der Polymerisation bei einem konstanten Niveau mit dem Katalysator kombiniert wird, wobei das resultierende Polypropylen eine Schmelzflussrate (MFR, 230°C/2, 16 kg) innerhalb eines Bereichs von 20 bis 500 g/10 min und einen Biegemodul von mindestens 250 kpsi (1720 MPa) (0,5 in/min ASTM D790(A)) aufweist.
- Verfahren nach Anspruch 10, bei der keine Nachreaktorverarbeitung des Polypropylens erfolgt, um die beanspruchten Eigenschaften zu erhalten.
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TWI729874B (zh) * | 2020-06-29 | 2021-06-01 | 臺灣塑膠工業股份有限公司 | 聚丙烯樹脂材料及其製作方法 |
WO2022035607A1 (en) | 2020-08-11 | 2022-02-17 | Exxonmobil Chemical Patents Inc. | Face masks incorporating elastomeric layers and methods of producing such face masks |
CN113214415B (zh) * | 2021-04-20 | 2022-07-26 | 国家能源集团宁夏煤业有限责任公司 | 复合外给电子体、烯烃聚合催化剂及其应用以及聚烯烃及其制备方法 |
WO2023192461A1 (en) * | 2022-04-01 | 2023-10-05 | Chevron U.S.A. Inc. | Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same |
US20240010927A1 (en) * | 2022-07-08 | 2024-01-11 | Chevron U.S.A. Inc. | Blend of waste plastic with bio feed and process of preparation |
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US6686433B1 (en) | 1994-02-04 | 2004-02-03 | Exxonmobil Chemical Patents Inc. | Dual donor catalyst system for the polymerization of olefins |
WO1996011982A1 (en) | 1994-10-12 | 1996-04-25 | Kimberly-Clark Worldwide, Inc. | Melt-extrudable thermoplastic polypropylene composition and nonwoven web prepared therefrom |
CN1116315C (zh) * | 1997-05-30 | 2003-07-30 | 株式会社宏大化纤 | 聚丙烯树脂组合物及注射成型制品 |
EP0942013B1 (de) | 1997-08-05 | 2004-02-04 | Mitsui Chemicals, Inc. | Polypropylenharzzusammensetzung und deren verwendung |
US6087459A (en) | 1998-05-14 | 2000-07-11 | Exxon Chemical Patents Inc. | Polymeric materials formed using blends of electron donors |
FI991057A0 (fi) | 1999-05-07 | 1999-05-07 | Borealis As | Korkean jäykkyyden propeenipolymeerit ja menetelmä niiden valmistamiseksi |
US6087750A (en) | 1999-05-18 | 2000-07-11 | Pacific Scientific Electro Kinetics Division | Permanent magnet generator |
US6809168B2 (en) | 1999-12-10 | 2004-10-26 | Exxonmobil Chemical Patents Inc. | Articles formed from propylene diene copolymers |
US7807769B2 (en) | 2002-09-20 | 2010-10-05 | Exxonmobil Chemical Patents Inc. | Isotactic polypropylene produced from supercritical polymerization process |
WO2005080497A1 (en) | 2004-02-12 | 2005-09-01 | Exxonmobil Chemical Patents Inc. | Polypropylene resin suitable for fibers and nonwovens |
US7678341B2 (en) | 2005-07-29 | 2010-03-16 | Exxonmobil Chemical Patents Inc. | Loop reactor heat removal |
ATE451421T1 (de) | 2005-12-22 | 2009-12-15 | Borealis Tech Oy | Polypropylenzusammensetzung enthaltend ein propylenhomopolymer |
WO2009007265A1 (en) | 2007-07-10 | 2009-01-15 | Basf Se | Stabilizer compositions |
EP2014707B1 (de) * | 2007-07-12 | 2014-04-23 | Borealis Technology Oy | Modifizierte Polymerzusammensetzungen, Modifikationsverfahren und Wirkstoffe zur Erzeugung freier Radikale für I.A.-Draht und Kabelanwendungen |
EP2386601B1 (de) | 2010-05-11 | 2012-07-04 | Borealis AG | Langkettiges, verzweigtes Polypropylen mit hoher Fließfähigkeit |
US9464178B2 (en) | 2012-10-31 | 2016-10-11 | Exxonmobil Chemical Patents Inc. | Articles comprising broad molecular weight distribution polypropylene resins |
WO2014070385A1 (en) * | 2012-10-31 | 2014-05-08 | Exxonmobil Chemical Patents Inc. | Articles comprising broad molecular weight distribution polypropylene resins |
JP6502530B2 (ja) | 2015-02-04 | 2019-04-17 | エクソンモービル ケミカル パテンツ インコーポレイテッド | バランスのとれた歪み硬化、溶融強度、およびずり減粘を有するポリプロピレン |
CN110785442B (zh) * | 2017-05-30 | 2022-05-13 | 埃克森美孚化学专利公司 | 具有高劲度和透明度的高熔体强度聚丙烯 |
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- 2018-05-09 KR KR1020197036144A patent/KR102325239B1/ko active IP Right Grant
- 2018-05-09 CN CN201880047131.1A patent/CN110914317B/zh active Active
- 2018-05-09 US US16/616,273 patent/US11459453B2/en active Active
- 2018-05-09 WO PCT/US2018/031804 patent/WO2018226345A1/en unknown
- 2018-05-09 EP EP18730483.7A patent/EP3635019B1/de active Active
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KR20190142412A (ko) | 2019-12-26 |
US20200172716A1 (en) | 2020-06-04 |
KR102325239B1 (ko) | 2021-11-10 |
CN110914317A (zh) | 2020-03-24 |
EP3635019A1 (de) | 2020-04-15 |
US11459453B2 (en) | 2022-10-04 |
CN110914317B (zh) | 2022-09-16 |
WO2018226345A1 (en) | 2018-12-13 |
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